Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
  • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
  • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
  • C09B62/08—Azo dyes
  • C09B62/09—Disazo or polyazo dyes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
  • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
  • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
  • C09B62/043—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring containing two or more triazine rings linked together by a non-chromophoric link

Definitions

• Reactive dyes are widely used for dyeing and printing textile fiber materials. Although a large number of usable reactive dyes with different properties and for different areas of application are available today, the technical status achieved, in view of the high requirements with regard to suitability for certain dyeing processes and the authenticity level of the dyeings, can in many cases still not be fully satisfactory.
• GB-A-869,279 discloses disazo dyes of the formula (3) given below, but they do not have the specific coupling components bearing the radicals R 4 and R 5 .
• DE-A-2,611,550 discloses fluorotriazinyl monoazo, metal complex azo or anthraquinone dyes doubled via a diamine.
• the object of the present invention is to find new reactive dyes which are suitable for dyeing and printing processes and which have a high degree of fixation and at the same time good washability of the non-fixed portions; furthermore, the dyes should generally have good fastness properties and in particular a shade in the orange range. It has been shown that the new dyes defined below largely fulfill the task.
• the invention therefore relates to reactive dyes of the formula or where X is fluorine or especially chlorine.
• the reactive dyes in which X is chlorine are very particularly preferred.
• Another object of the invention are reactive dyes of the formula in which R 4 is hydrogen, methoxy or ureido, R 5 is hydrogen, methyl or methoxy, X is fluorine or chlorine and Z is an aliphatic, araliphatic, aromatic or heterocyclic amino group free of fiber-reactive radicals.
• suitable amino groups Z are: alkylamino, N, N-dialkylamino, cycloalkylamino, N, N-dicycloalkylamino, aralkylamino, arylamino groups, mixed substituted amino groups, such as N-alkyl-N-cyclohexylamino and N-alkyl -N-arylamino groups, furthermore amino groups which contain heterocyclic radicals, which may have further fused-on carbocyclic rings, and amino groups, in which the amino nitrogen atom is a member of an N-heterocyclic ring which optionally contains further heteroatoms.
• alkyl radicals can be straight-chain or branched, low molecular weight or higher molecular weight; alkyl radicals having 1 to 6 carbon atoms are preferred; suitable cycloalkyl, aralkyl and aryl radicals are, in particular, cyclohexyl, benzyl, phenethyl, phenyl and naphthyl radicals; heterocyclic radicals are primarily furan, thiophene, pyrazole, pyridine, pyrimidine, quinoline, Benzimidazole, benzthiazole and benzoxazole residues; and as amino groups in which the amino nitrogen atom is a member of an N-heterocyclic ring, preference is given to residues of six-membered N-heterocyclic compounds which may contain nitrogen, oxygen and sulfur as further heteroatoms.
• alkyl, cycloalky, aralkyl and aryl radicals, the heterocyclic radicals and the N-heterocyclic rings can be further substituted, for example by: halogen, such as fluorine, chlorine and bromine, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C. 1 -C 4 alkyl, C 1 -C 4 alkoxy, acylamino groups such as acetylamino, ureido, hydroxy, carboxy, sulfomethyl and sulfo.
• halogen such as fluorine, chlorine and bromine, nitro, cyano, trifluoromethyl
• sulfamoyl carbamoyl
• C. 1 -C 4 alkyl C 1 -C 4 alkoxy
• acylamino groups such as acetylamino, ureido, hydroxy, carboxy, sulfomethyl and
• radical Z in formula (3) examples are: -NH 2 , methylamino, ethylamino, propylamino, isopropylamino, butylamino, ⁇ - (acetylamino) ethylamino, hexylamino, ⁇ -methoxyethylamino, y-methoxypropylamino, ⁇ -ethoxyethylamino, N.
• Reactive dyes of the formula (3) are preferred in which Z is an aromatic amino group, in particular a sulfo or disulfophenylamino group.
• the reactive dyes of the formula are very particularly preferred where X is fluorine or especially chlorine.
• the preparation of the reactive dyes of the formula (3) is characterized in that an aminodisazo compound of the formula with a triazine of the formula and an amine of the formula HZ (8) condensed with one another in any order, where R 4 , R 5 , X and Z have the meanings given under the formula (3).
• the reactive dyes of the formulas (4a) and (5a) are prepared in such a way that at least twice the molar amount of the aminodisazo compound of the formula or with twice the molar amount of triazine of the formula and a molar amount of 1,2-ethylenediamine condensed with one another in any order, where X is chlorine or fluorine.
• reaction is carried out step by step, the sequence of the simple reactions between the individual reaction components advantageously depending on the particular conditions.
• One embodiment of the process according to the invention is characterized in that an aminodisazo compound of the formula (6) or (6a) or (6b) is condensed with a triazine of the formula (7) and the primary condensation product obtained with an amine of the formula (8) or condensed with 1,2-ethylenediamine.
• a further embodiment of the process according to the invention is characterized in that an aminodisazo compound of the formula (6) or (6a) or (6b) with a primary condensation product of a triazine of the formula (7) and an amine of the formula (8) or condensed with 1,2-ethylenediamine.
• Ammonia methylamine, dimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, butylamine, dibutylamine, isobutylamine, sec.-butylamine, tert.-butylamine, hexylamine, methoxyethylamine, ethoxyethylamine, methoxypropylamine, chloroethylamine, hydroxyethylamine, dihydroxyethylamine, hydroxypropylamine, hydroxypropylamine, hydroxypropylamine (Acetylamino) ethylamine, enzylamine, phenethylamine, cyclohexylamine, N-propylaminobenzene, N-isopropylaminobenzene, N-butylaminobenzene, N-isobutylaminobenzene, N-sec.-butylaminobenzene, N-hex
• the diazo components are generally diazotized by the action of nitrous acid in aqueous mineral acid solution at low temperature, and the coupling to the coupling components at weakly acidic, neutral to weakly alkaline pH values.
• the condensation of the 2,4,6-trichloro- or 2,4,6-trifluoro-s-triazine of the formula (7) with the aminodisazo compounds and the amino compounds of the formula (8) are preferably carried out in aqueous solution or suspension, at low temperature and at a weakly acidic, neutral to weakly alkaline pH value, so that in the finished reactive dye of the formula (3), (4a) or (5a) there is still a chlorine or fluorine atom remaining as a detachable residue.
• the hydrogen chloride or hydrogen fluoride liberated during the condensation is advantageously continuously neutralized by adding aqueous alkali metal hydroxides, carbonates or bicarbonates. Isolation of the dichloro or difluorotriazine azo compound is generally dispensed with.
• the reactive dyes of the formula (3), (4a) or (5a) can be isolated and processed into useful, dry dye preparations.
• the isolation is preferably carried out at the lowest possible temperatures by salting out and filtering.
• the filtered dyes can optionally be added after the addition of couping agents and / or buffering agents, e.g. after adding a mixture of equal parts of mono- and disodium phosphate, dried; drying is preferably carried out at temperatures which are not too high and under reduced pressure.
• the dry preparations according to the invention can be spray-dried directly by spray-drying the entire preparation mixture, i.e. Manufacture without intermediate insulation of the dyes.
• Also of interest are storage-stable, concentrated liquid dye preparations of the reactive dyes of the formula (3), (4a) or (5a) and their use for the production of padding liquors, dyebaths and, above all, printing pastes which are used for dyeing and printing fiber materials, in particular cellulose-containing fiber materials .
• Liquid dye preparations have advantages over the powder form, e.g. No dust development when preparing printing pastes and padding and dyeing liquors, no wetting problems due to lump formation, no stained stains due to undissolved dye particles.
• Such liquid formulations should be highly concentrated (at least 10% by weight and preferably more than 15% by weight of dye) and should remain stable for at least several months in a wide temperature range (-10 to + 40 ° C).
• the starting solution or suspension for the preparation of the dye preparations can be the aqueous solution or suspension which may have been obtained directly from the synthesis or an aqueous suspension of the moist press or filter cakes of the raw dyes of different content of undesired dissolved substances with low molecular weight, especially use of by-products and dissolved inorganic and organic salts in the synthesis of the dye.
• the crude condensation or neutralization solution can also be used directly.
• Starting solutions or suspensions containing 2 to 50% of dye are advantageously used.
• Concentrated liquid preparations are usually real or colloidal solutions. They are thin (viscosity of about 5 to 300 cp / 20 ° C) and have a good shelf life, i.e. they remain in a usable state for at least several months at temperatures from -20 to + 60 ° C, in particular -10 to + 40 ° C.
• these preparations can be mixed with water and also with organic solvents and / or thickeners without the dye precipitating or without other inhomogeneities.
• the liquid dye preparations preferably contain 20 to 50 percent by weight, in particular 35 to 45 percent by weight, of the dye of the formula (3), (4a) or (5a).
• the stable, concentrated liquid dye preparations are particularly suitable for the production of printing pastes for printing cellulose fiber materials and for continuous dyeing processes.
• a method for producing a liquid preparation according to the invention is e.g. from EP-A-0 333 656, in which the dye solution is desalted and concentrated on a system for reverse osmosis.
• the dye suspension is then desalted and concentrated, if necessary after dilution with water, and finally converted into a liquid or solid dye preparation ready for sale.
• the dye solutions used generally have a dye content of 5 to 20% by weight and a salt content (inorganic salts) of 1 to 20% by weight, in particular 1 to 10% by weight.
• the pH is generally in the range from 3 to 10, preferably from 3 to 9. Insoluble constituents are removed by microfiltration, and the concentration and desalination are carried out until a dye content of 10 to 50% by weight is reached.
• the salt content drops below 5% by weight, e.g. 0.05 to 5% by weight, and preferably less than 1% by weight, e.g. 0.05 to 1% by weight.
• the concentrated aqueous dye preparation is, if appropriate after adding the components customary for liquid formulations, such as solubilizers, foam suppressants, antifreezes, humectants, surfactants, buffer substances and / or antimicrobials and adjusting the pH, only by diluting and / or or to bring to a predetermined final dye content with the help of coupé agents.
• solubilizers foam suppressants, antifreezes, humectants, surfactants, buffer substances and / or antimicrobials and adjusting the pH, only by diluting and / or or to bring to a predetermined final dye content with the help of coupé agents.
• the dye preparation can, if appropriate after addition of additives, such as binders, dedusting agents, wetting agents, buffer substances, such as alkali polyphosphates, disodium hydrogenphosphate, citric acid and / or ethylenediaminetetraacetic acid, and / or coupé agents, be converted into a solid dye preparation by dehydration. Thanks to the increased dye concentration, less energy is required to dry. Usual drying processes are used, especially spray drying.
• the pH of the ready-to-use liquid formulation of the reactive dyes is generally adjusted by adding buffer substances.
• the pH is approximately in the range from 7.0 to 8.5, preferably 8.0.
• auxiliaries or additives mentioned can of course not only be added to the dye solution as a commercial form before their final formulation, but can also be introduced into the raw dye solution before or during the process according to the invention and are therefore at least partially already in the dye solution from which the final ready-to-use product is made Dye formulation is produced, available (e.g. solubilizers, solvents, surfactants etc.). There is an addition during the procedure Of course, this only makes sense if the auxiliary agent or additives are not completely removed from the solution again by one of the membrane separation processes.
• the concentrated liquid preparations of the reactive dyes of formula (3), (4a) or (5a) thus contain 10 to 50% by weight of dye, 0.05 to 5% by weight of an inorganic salt, e.g. NaCl, KCl, LiCl, as much buffer substances, e.g. Mono- and disodium phosphate or sodium tripolyphosphate or mixtures of buffer substances so that a pH between 7.0 and 8.5 can be set, as well as water.
• an inorganic salt e.g. NaCl, KCl, LiCl
• buffer substances e.g. Mono- and disodium phosphate or sodium tripolyphosphate or mixtures of buffer substances so that a pH between 7.0 and 8.5 can be set, as well as water.
• the reactive dyes of the formula (3), (4a) or (5a) are notable for high reactivity and they give dyeings with good wet and light fastness. It is particularly noteworthy that the dyes have good solubility and high dye fixation, that they diffuse well in the cellulose fiber and that the non-fixed portions can be easily removed.
• the dyes of the formula (3), (4a) or (5a) according to the invention are either in the form of their free acid or, preferably, as their salts.
• Suitable salts are, for example, alkali, alkaline earth or ammonium salts or the salts of an organic amine. Examples include the sodium, lithium, potassium or ammonium salts or the salt of triethanolamine.
• the reactive dyes of the formula (3), (4a) or (5a) are suitable for dyeing and printing a wide variety of materials, such as silk, leather, wool, polyamide fibers and polyurethanes, but in particular cellulosic materials with a fibrous structure, such as linen, cellulose, regenerated cellulose and especially cotton. They are suitable both for the exhaust process and for dyeing according to the pad dyeing process, according to which the goods are impregnated with aqueous and, if appropriate, also salt-containing dye solutions, and the dyes are fixed after an alkali treatment or in the presence of alkali, if appropriate with the action of heat.
• They are particularly suitable for printing textile-containing cellulose-containing fiber materials, in particular cotton, but also for printing nitrogen-containing fibers, for example mixed fabrics containing wool, silk or wool. They are particularly suitable for gentle printing processes, such as with sodium propionate as fixing alkali.
• the dyes according to the invention are advantageously used as liquid dyeing or printing preparations.
• the parts mean parts by weight.
• the temperatures are degrees Celsius.
• the relationship between parts by weight and parts by volume is the same as that between grams and cubic centimeters.
• the reactive dye is precipitated by adding NaCl, isolated and dried in vacuo.
• the reactive dye obtained corresponds in the form of the free acid to the formula It dyes cotton from an aqueous liquor in real orange tones.
• Example 2 parts of the dye obtained in Example 1 are dissolved in 20 parts of water at 20 to 50 ° C. with the addition of 5 to 20 parts of urea and 2 parts of anhydrous Na 2 CO 3 .
• a cotton fabric is impregnated with the solution obtained so that it increases by 60 to 80% of its weight, and then dried.
• the mixture is then heat-set at 140 to 210 ° C. for 1 1/2 to 5 minutes, then soaped for a quarter of an hour in a 0.1% solution of an ion-free detergent at boiling temperature, rinsed and dried.
• Example 2 parts of the dye obtained in Example 1 are dissolved in 2000 parts of water with the addition of 120 parts of NaCl or anhydrous Na 2 SO 4 at 75 ° C. You go into this dye bath with 100 parts of a cotton fabric and keep the temperature constant for 30 to 60 minutes. Then 10 parts of anhydrous Na 2 CO 3 and 4 ml of sodium hydroxide solution (36%) are added. The temperature is kept at 75 to 80 ° C. for a further 45 to 60 minutes, then soaped in a 0.1% solution of an ion-free detergent at boiling temperature for 15 minutes, rinsed and dried.
• Example 2 parts of the dye obtained in Example 1 are dissolved in 100 parts of water with the addition of 0.5 part of sodium m-nitrobenzenesulfonate.
• a cotton fabric is impregnated with the solution obtained so that it increases by 75% in weight, and then dried. Then the fabric is impregnated with a solution at 20 ° C., which contains 5 g of sodium hydroxide and 300 g of sodium chloride per liter, squeezed to 75% weight gain, the dyeing is dampened for 30 seconds at 100 to 101 ° C., rinsed and soaped during one Quarter of an hour in a 0.3% solution of an ion-free detergent at boiling temperature, rinses and dries.
• Example 2 parts of the dye obtained in Example 1 are dissolved in 100 parts of water.
• the solution is added to 1900 parts of cold water, 60 parts of sodium chloride are added and 100 parts of a cotton fabric are added to this dye bath.
• the temperature is raised to 60 ° C., after 30 minutes 40 parts of anhydrous Na 2 CO 3 and another 60 parts of sodium chloride are added.
• the temperature is kept at 60 ° C. for 30 minutes, rinsed and then the dyeing is soaped in a 0.3% solution for 15 minutes Solution of an ion-free detergent at boiling temperature, rinses and dries.

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